US7776242B2 - Method for granulating flexible polyolefin resin and granule - Google Patents

Method for granulating flexible polyolefin resin and granule Download PDF

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US7776242B2
US7776242B2 US11/908,413 US90841306A US7776242B2 US 7776242 B2 US7776242 B2 US 7776242B2 US 90841306 A US90841306 A US 90841306A US 7776242 B2 US7776242 B2 US 7776242B2
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resin
granulating
polyolefin resin
flexible polyolefin
melting point
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US20090057935A1 (en
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Yoshinori Sato
Shoichi Yuzaki
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Idemitsu Kosan Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/001—Removal of residual monomers by physical means
    • C08F6/005—Removal of residual monomers by physical means from solid polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • the invention relates to a method for granulating a flexible polyolefin resin.
  • the invention relates to a method for granulating a flexible polyolefin resin which can reduce tackiness of the flexible polyolefin resin and prevent blocking of the granules.
  • the invention relates to a method for granulating a flexible polyolefin resin which can prevent refusion of the granules after granulating.
  • Flexible polyolefin resins are widely used as raw materials for films and the like as a substitute for a flexible vinyl chloride resin with a large environmental load.
  • a flexible polyolefin resin contains a large amount of low molecular weight components by its nature, the surface of granules made of the resin may exhibit tackiness. Therefore, when a polymerized flexible polyolefin resin is granulated into granules with a size easy to handle, there has been a problem that granules tend to adhere among themselves and form lumps (blocks). Furthermore, refusion of granules is easily conducted after granulation.
  • the inventors of the present invention have found that a tacky feeling of granules of a flexible polyolefin resin can be reduced by melting the resin, and granulating the resin after stirring and kneading the molten resin while cooling the molten resin to a temperature below the melting point.
  • the inventors then filed a patent application directing to the above finding (Patent document 2).
  • Patent Document 1 JP-A-H7-88839
  • Patent Document 2 JP-A-2005-179556
  • the method of Patent document 2 cools the polymerized resins and thereafter heats the resins again for melting, which results in low productivity.
  • the method is thus desired to be further improved.
  • the method of Patent document 2 requires expensive facilities such as a kneader to stir and knead a molten resin while cooling the molten resin after melting the resin.
  • pellets float in a cooling water pool in some granulation methods, the cooling efficiency of the method of Patent document 2 is impaired. Therefore, further improvement has been demanded for higher granule productivity.
  • an object of the invention is to provide a method for efficiently granulating a flexible polyolefin resin.
  • An object of the invention is to provide an efficient granulating method without refusion of granules after granulation.
  • the inventors have found that the tackiness of a flexible polyolefin resin granules can be reduced by cooling a molten flexible polyolefin resin after polymerization and volatilization to a certain temperature, and then granulating the resin by an underwater granulation method.
  • the inventors have found that a cooling efficiency can be improved since the resin can also be cooled when transporting it to a post-granulating process (dewatering process).
  • a method for granulating a flexible polyolefin resin comprising:
  • the polypropylene has a melting point (Tm-D) of 20 to 120° C.
  • PB isotacticity ((mmmm)/(mmrr+rmmr)) is 20 or less.
  • the method for granulating a flexible polyolefin resin of the invention utilizes heat of a volatilization process and involves an underwater granulation method excelling in cooling efficiency, the method has high productivity.
  • the method of the invention has a high cooling efficiency at granulation, leading to downsizing of facilities.
  • the method of the invention enhances utility value of a product due to no refusion of granules after granulating.
  • FIG. 1 is a flow chart for illustrating the granulation method of the invention.
  • FIG. 2 is a schematic drawing for illustrating an underwater granulation method.
  • FIG. 1 is a flow chart for illustrating the granulating method of the invention.
  • An olefin monomer which is a raw material, undergoes a known polymerization such as solution polymerization and vapor phase polymerization to be a flexible polyolefin resin.
  • the flexible polyolefin resin obtained is heated and volatilized to remove a solvent, an unreacted monomer component and the like therefrom. Since the temperature of the volatilization process is usually about 100° C. to about 250° C., the resin is in a molten state. In the invention, the molten resin is directly transported to a cooling process. This eliminates the need of reheating processes of the resin, whereby productivity can be improved.
  • the volatilization process can be carried out with usual apparatuses such as a melting vessel.
  • the molten resin can be transported through pipe lines with transporting means such as a gear pump.
  • the molten flexible polyolefin resin is cooled to a temperature in a range of the melting point of the resin (Tm-D) ⁇ 50° C., preferably (Tm-D) ⁇ 20° C., followed by granulating.
  • Tm-D melting point of the resin
  • Tm-D melting point of the resin
  • the melting point of the resin is defined as the peaktop of the peak observed on the highest temperature side of a fusion endothermic curve obtained by heating 10 mg of a sample at a rate of 10° C./min after being retained at 10° C. for 5 minutes in a nitrogen atmosphere measured by using a differential scanning calorimeter (DSC).
  • a polymer cooler As the apparatuses for cooling the resin, a polymer cooler, kneader equipped with a jacket, polymer mixer equipped with a jacket and the like can be used.
  • the polymer cooler is preferably used since the box is relatively low cost and can reduce the equipment cost.
  • FIG. 2 is a schematic drawing for illustrating an underwater granulation method.
  • a resin cooled with a cooler 11 passes through a dice 12 with at least one hole having a specific shape provided at an end of the cooler 11 , and is then cut into a pellet shape with a cutting chamber 13 .
  • the cutting chamber 13 cuts a resin with a cutting edge which spins at a high speed.
  • the cooling water in the chamber 13 circulates in the chamber 13 , a dewaterer 14 and a cooling water tank 15 .
  • the cut pellets are transported to the dewaterer 14 from the chamber 13 with the circulating water. Subsequently, the pellet resin and the cooling water are separated with the dewaterer 14 , and then the pellets are recovered.
  • the underwater granulation method can efficiently cool the cut resin pellets with a water stream without floating of pellets on a water surface, whereby cooling facilities can be downsized.
  • the temperature of the cooling water of the underwater granulation method is set at 30° C. or less.
  • the temperature of the cooling water is preferably 20° C. or less, more preferably 15° C. or less.
  • the pellets may adhere among themselves and form lumps due to insufficient cooling of the resin at granulation.
  • the temperature of the cooling water can be adjusted with a heat media cooler or a heat media heater (not shown).
  • an antifusion agent is added into the cooling water.
  • silicone and the like can be used.
  • the amount of the antifusion agent added may be appropriately adjusted depending on the type of the antifusion agent used.
  • the amount of the antifusion agent added in the cooling water is 100 wtppm to 5000 wtppm, preferably 500 wtppm to 1000 wtppm.
  • the rotation speed of the cutting edge of the cutting chamber is generally 1 to 20 m/s, preferably 1 to 10 m/s.
  • a polymer obtained by polymerizing an ⁇ -olefin with 3 to 20 carbon atoms using a metallocene catalyst is particularly preferable. This is because the polymer obtained by polymerization using a metallocene catalyst has a uniform molecular weight and composition distribution to contain only a very small amount of components that induce crystal nuclei, and has flowability even when the polymer is cooled with a cooler.
  • the ⁇ -olefin with 3 to 20 carbon atoms propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like can be given.
  • the flexible polyolefin resin may be either a homopolymer of these ⁇ -olefins or a copolymer of these ⁇ -olefins.
  • the copolymer may contain ethylene in addition to the above ⁇ -olefins.
  • Preferable polymers are propylene-based polymers and 1-butene-based polymers.
  • the metallocene-type flexible polyolefin resin can be produced by polymerizing the above-mentioned ⁇ -olefins in the presence of a metallocene catalyst consisting of a transition metal compound of the group 4 of the periodic table containing cyclopentadienyl rings and methylaluminoxane, or a compound forming an ion complex by the reaction with the transition metal compound of the group 4 of the periodic table and an organoaluminum compound.
  • a metallocene catalyst consisting of a transition metal compound of the group 4 of the periodic table containing cyclopentadienyl rings and methylaluminoxane
  • a compound of zirconium, titanium, or hafnium containing a multidentate coordination compound as a ligand in which at least two groups selected from the group consisting of cycloalkadienyl groups or substituted derivatives thereof, specifically, an indenyl group, substituted indenyl groups, and its partial hydrides are bonded with each other via a lower alkylene group or silylene group, can be given.
  • transition metal compounds include stereorigid chiral compounds of zirconium and hafnium such as ethylene-bis-(indenyl)zirconium dichloride reported by H. H. Brintzinger et al in J. Organometal. Chem., 288, 63 (1985), ethylene-bis-(indenyl)hafnium dichloride described in J. Am. Chem. Soc., 109, 6544 (1987), dimethylsilylbis(2,4-dimethylcyclopentadienyl)zirconium dichloride, dimethylsilylbis(2,4,5-trimethylcyclopentadienyl)zirconium dichloride, or hafnium dichloride of these complexes reported by H. Yamazaki et al, in Chemistry Letters, 1853 (1989).
  • ethylenebis(indenyl)zirconium dichloride ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, ethylenebis(4-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methyl-1-indenyl)zirconium dichloride, ethylenebis(6-methyl-1-indenyl)zirconium dichloride, ethylenebis(7-methyl-1-indenyl)zirconium dichloride, ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(indenyl)hafnium dichloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)hafnium dichloride, ethylenebis(4-methyl-1-indenyl)ha
  • tetra(pentafluorophenyl)borate anion-containing compounds such as triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, and lithium tetrakis(pentafluorophenyl)borate
  • tetra(pentafluorophenyl)aluminate anion-containing compounds such as triphenylcarbenium tetrakis(pentafluorophenyl)aluminate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)aluminate, and lithium tetrakis(pentafluoropheny
  • organoaluminum compound compounds having at least one Al—C bond in the molecule can be given.
  • organoaluminum compounds trialkylaluminums such as triethylaluminum, triisobutylaluminum, and trihexylaluminum, dialkylaluminum halides such as diethylaluminum halide and diisobutylaluminum halide, a mixture of trialkylaluminum and dialkylaluminum halide, and alkylalmoxanes such as tetraethyldialmoxane and tetrabutylalmoxane can be given.
  • organoaluminum compounds trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, and alkylalmoxane are preferable, with particularly preferable organoaluminum compounds being triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride, and tetraethyldialmoxane.
  • organoaluminum triethylaluminum, triisobutylaluminum, and the like are preferably used.
  • These metallocene catalysts and/or co-catalysts may be used carried on a carrier.
  • organic compounds such as polystyrene and inorganic oxides such as silica and alumina can be given.
  • any of a mass polymerization method, solution polymerization method, vapor phase polymerization method, suspension polymerization method, and the like can be given, and either a batch system or continuous system can be used.
  • Preliminary polymerization using a small amount of ⁇ -olefins such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene may be carried out.
  • the reaction is carried out usually at a temperature of ⁇ 50 to 250° C., and preferably 0 to 150° C., usually for 1 to 10 hours under a pressure usually from atmospheric pressure to 300 kg/cm 2 -G.
  • the granulation method of the invention can be in particular preferably applied to the flexible polyolefin resin having the following properties:
  • Tm-D the melting point of the flexible polyolefin resin
  • the melting point (Tm-D) is preferably 50 to 100° C., and more preferably 60 to 90° C.
  • the crystallization time is preferably three minutes or more. If the crystallization time is less than three minutes, the effect of promoting crystallization is small.
  • the crystallization time is preferably five minutes or more, and more preferably ten minutes or more.
  • the crystallization time is measured with a differential scanning calorimeter as follows: A sample is maintained in a molten state at 190° C. for three minutes in a nitrogen atmosphere, rapidly quenched to 25° C. at a rate of about 300° C./min. by introducing liquid nitrogen, and maintained at this temperature.
  • the crystallization time refers to the period of time from when the sample is cooled to 25° C. until the crystallization exothermic peak is observed.
  • the melting point (Tm-D) and crystallization time of the flexible polyolefin resin can be controlled by adjusting the isotacticity mentioned later.
  • the flexible polyolefin resin is preferably polypropylene with a PP isotacticity [mm] of 50 to 90 mol %. If less than 50 mol %, the resin may exhibit tackiness; if more than 90 mol %, processability may decrease.
  • the PP isotacticity [mm] is preferably 50 to 80 mol %, and more preferably 60 to 80 mol %.
  • the PP isotacticity [mm] in the invention refers to a value determined by a method proposed by A. Zambelli et al. in Macromolecules, 6925 (1973).
  • the flexible polyolefin resin is preferably a 1-butene polymer having a PB isotacticity of ((mmmm)/(mmrr+rmmr)) of 20 or less. If the PB isotacticity exceeds 20, flexibility is reduced and the processability is impaired.
  • the 1-butene polymer preferably has the following properties of (1) and (2):
  • Tm-D melting point of the 1-butene polymer
  • the 1-butene polymer preferably further has the following property of (4):
  • PB isotacticity ((mmmm)/(mmrr+rmmr)) is 20 or less.
  • the PB isotacticity of ((mmmm)/(mmrr+rmmr)) is calculated from the mesopentad fraction (mmmm) and abnormal insertion content (1, 4 insertion fraction).
  • the mesopentad fraction (mmmm) and abnormal insertion content (1, 4 insertion fraction) are measured according to the methods reported by Asakura et al. (Polymer Journal, 16, 717 (1984)), J. Randall et al. (Macromol. Chem. Phys., C29, 201 (1989)), and V. Busico et al. (Macromol. Chem. Phys., 198, 1257 (1997)).
  • the method includes measuring the signals of the methylene group and methine group using 13 C-NMR spectrum, determining the mesopentad fraction and abnormal insertion content in a poly(1-butene) molecule, and calculating the PB isotacticity of ((mmmm)/(mmrr+rmmr)).
  • the PP isotacticity [mm] and PB isotacticity ((mmmm)/(mmrr+rmmr)) can be controlled by adjusting the type of catalyst, polymerization temperature, and monomer concentration.
  • the granules of the flexible polyolefin resin preferably remain left at a specific temperature for a specific time after granulation. This residence treatment can suppress the refusion of the granules which occurs after granulation.
  • a common vessel, tubing and the like can be used as the facility for retaining the granules.
  • the vessel desirably has a large surface area to prevent the refusion of the granules floating on the surface of the vessel.
  • stirring in the vessel is desired.
  • many tiered vessels be connected in series to prevent short pass.
  • the tubing desirably has an enough length to give a certain residence time. In the case where the tubing has too long a length to get in the way of the layout of the facility, the tubing may be wound like a coil or bundle together.
  • the vessel and tubing are preferably provided with a temperature adjusting system such that the both are set at the optimum temperature which promotes the crystallization.
  • a water vessel is preferable from the view point of cost and the like.
  • gas such as air and nitrogen also can be used in addition to water which is easy for industrial use.
  • an antifusion agent may be added therein.
  • the residence time is 5 minutes or more and 24 hours or less to promote sufficient crystallization.
  • the residence time is less than 5 minutes, the crystallization may be insufficient.
  • the resin is sufficientially crystallized in 24 hours and, therefore, the residence time exceeding 24 hours leads to waste of the facility and increasing of cost.
  • the temperature of the residence treatment which is the temperature of water when a water vessel is used for the facility for example, is 0° C. or more and 50° C. or less to promote the crystallization.
  • the temperature of the residence treatment is less than 0° C., water undesirably turns to ice.
  • the temperature of the residence treatment is more than 50° C., the crystallization rate is undesirably slow.
  • the properties of the resins polymerized in the preparation examples were measured according to the following methods.
  • Mw mass average molecular weight
  • Mn number average molecular weight
  • the lithium salt obtained above was dissolved in 50 ml of toluene in a nitrogen stream. After cooling the solution to ⁇ 78° C., a suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride in toluene (20 ml) which was previously cooled to ⁇ 78° C. was added dropwise. After the addition, the mixture was stirred at room temperature for six hours. The solvent was evaporated from the reaction solution.
  • a stainless steel reactor with an internal volume of 0.20 m 3 equipped with a stirrer was continuously charged with n-heptane at a rate of 30 l/hr, triisobutylaluminum (manufactured by Nippon Aluminum Alkyls, Ltd.) at 15 mmol/hr, methylaluminoxane (manufactured by Albemarle Corp.) at 15 mmol/hr, and (1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-trimethylsilylmethylindenyl)zirconium dichloride obtained in the Preparation Example at 15 ⁇ mol/hr.
  • Polypropylene was obtained by polymerizing while continuously supplying propylene and hydrogen under the conditions of a polymerization temperature of 60° C., a gas phase hydrogen concentration of 50 mol %, and a total pressure in the reactor of 0.7 MPaG.
  • the molten resin was transported using a transporting pump to a polymer mixer equipped with a jacket (L84-VPR-3.7 manufactured by SATAKE CO., LTD.)
  • the resin was cooled to 65° C. in the polymer mixer, followed by underwater granulation with a granulator.
  • PASC-21HS manufactured by TANABE PLASTICS MACHINERY CO., LTD. was used as the granulator, the temperature of cooling water was 10° C., and the circumferential velocity of cutter was 3.8 m/s.
  • Silicone (X-22-904 manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the cooling water to a concentration of 600 wtppm.
  • the resulting metallocene polypropylene was evaluated to confirm that the molecular weight distribution (Mw/Mn) was 1.8, the molecular weight (Mw) was 33,000, the PP isotacticity [mm] was 67 mol %, the glass transition temperature (Tg) was ⁇ 4° C., and the melting point (Tm-D) was 70° C. The crystallization time was 6 minutes.
  • Polypropylene was granulated in the same manner as in Example 1 except that the resin was not cooled in the polymer mixer and the temperature of the polypropylene was 150° C. at the outlet of the polymer mixer.
  • Polypropylene was granulated in the same manner as in Example 1 except that silicone was not added.
  • Polypropylene was granulated in the same manner as in Example 1 except that the temperature of the cooling water was 40° C.
  • a stainless steel reactor with an internal volume of 0.20 m 3 equipped with a stirrer was continuously charged with n-heptane at a rate of 20 l/hr, triisobutylaluminum (manufactured by Nippon Aluminum Alkyls, Ltd.) at 16 mmol/hr, methylaluminoxane (manufactured by Albemarle Corp.) at 17 mmol/hr, and (1,2′-dimethylsilylene)(2,1′-dimethylsilylene)-bis(3-trimethylsilylmethylindenyl)zirconium chloride obtained in the Preparation Example at 17 ⁇ mol/hr.
  • Polybutene-1 was obtained by polymerizing while continuously supplying 1-butene and hydrogen under the conditions of a polymerization temperature of 60° C., a gas phase hydrogen concentration of 50 mol %, and a total pressure in the reactor of 0.7 MPaG.
  • the resulting metallocene polybutene-1 was evaluated to confirm that the molecular weight distribution (Mw/Mn) was 1.8, the molecular weight (Mw) was 70,000, the PB isotacticity ((mmmm)/(mmrr+rmmr)) was 8.2, the glass transition temperature (Tg) was ⁇ 29° C., and the melting point (Tm-D) was 71° C. The crystallization time was 30 minutes or more.
  • Example 1 The pellets obtained in Example 1 were collected in a water vessel where the temperature of water was 13° C., followed by residence for 40 minutes. Then the pellets were removed and the following evaluation experiment for refusion was conducted.
  • the removed pellets were put in a cell with a cross-sectional area of 60 mm ⁇ 60 mm and a height of 70 mm.
  • a lid with a weight of 330 g was put on the upper surface of the cell, and then a weight with 5,000 g was put on the lid, followed by allowing to stand for 90 minutes 50° C.
  • the evaluation experiment for refusion was conducted in the same manner as in Example 3 except that the residence time was 3 minutes. As a result, the refusion of the pellets was observed.
  • the evaluation experiment for refusion was conducted in the same manner as in Example 3 except that the temperature of water was 80° C. As a result, the refusion of the pellets was observed.
  • Example 2 The pellets obtained in Example 2 were collected in a water vessel where the temperature of water was 13° C., followed by residence for 40 minutes. Then the pellets were removed and the following evaluation experiment for refusion was conducted.
  • the removed pellets were put in a cell with a cross-sectional area of 60 mm ⁇ 60 mm and a height of 70 mm.
  • a lid with a weight of 330 g was put on the upper surface of the cell, and then a weight with 5,000 g was put on the lid, followed by allowing to stand for 90 minutes 50° C.
  • the invention can provide a method for granulating a flexible polyolefin resin with high productivity by utilizing heat of a volatilization process and using an underwater granulation method excelling in cooling efficiency.
  • the invention can provide an efficient method for granulating a flexible polyolefin resin without refusion.

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US20130317193A1 (en) * 2012-05-24 2013-11-28 Henkel Corporation Process for preparing flowable amorphous poly-alpha olefin adhesive pellets
WO2014190098A1 (en) 2013-05-23 2014-11-27 Bostik, Inc. Hot melt adhesive based on low melting point polypropylene homopolymers
WO2018098431A1 (en) 2016-11-28 2018-05-31 Bostik, Inc. Hot melt adhesives for bonding elastomeric components, nonwoven materials, and thermoplastic films
EP3155020B1 (en) 2014-06-12 2019-03-27 Dow Global Technologies LLC An improved process for producing pelletized polymer compositions
US10759978B2 (en) 2014-10-13 2020-09-01 Bostik, Inc. Polyolefin-based hot melt adhesives with improved processing and bonding performance
WO2021011390A1 (en) 2019-07-12 2021-01-21 Bostik, Inc. Tackifier-free hot melt adhesive compositions suitable for use in a disposable hygiene article

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CN101397512B (zh) * 2007-09-25 2012-01-11 中国石油天然气股份有限公司 一种石蜡水下造粒生产方法
KR101138928B1 (ko) * 2009-06-19 2012-04-30 듀폰-미츠이 폴리케미칼 가부시키가이샤 수지 펠릿 및 그 제조 방법
US9308672B2 (en) 2011-03-01 2016-04-12 E I Du Pont De Nemours And Company Process for preparing pellets of poly(trimethylene terephthalate)
JP6591201B2 (ja) * 2015-05-28 2019-10-16 出光興産株式会社 軟質樹脂の造粒方法
JP6494423B2 (ja) * 2015-05-28 2019-04-03 出光興産株式会社 軟質樹脂の造粒物の貯蔵方法

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US9334431B2 (en) 2013-05-23 2016-05-10 Bostik, Inc. Hot melt adhesive based on low melting point polypropylene homopolymers
WO2014190098A1 (en) 2013-05-23 2014-11-27 Bostik, Inc. Hot melt adhesive based on low melting point polypropylene homopolymers
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WO2018098431A1 (en) 2016-11-28 2018-05-31 Bostik, Inc. Hot melt adhesives for bonding elastomeric components, nonwoven materials, and thermoplastic films
WO2021011390A1 (en) 2019-07-12 2021-01-21 Bostik, Inc. Tackifier-free hot melt adhesive compositions suitable for use in a disposable hygiene article

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EP1876000B1 (en) 2017-01-25
EP1876000B2 (en) 2020-04-15

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